US4657779A - Shrinkage-resistant ultraviolet-curing coatings - Google Patents
Shrinkage-resistant ultraviolet-curing coatings Download PDFInfo
- Publication number
- US4657779A US4657779A US06/841,216 US84121686A US4657779A US 4657779 A US4657779 A US 4657779A US 84121686 A US84121686 A US 84121686A US 4657779 A US4657779 A US 4657779A
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- ultraviolet
- coating composition
- monoacrylate
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- liquid coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
- C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Definitions
- This invention relates to liquid ultraviolet-curable coating compositions which cure to a solid adherent film with minimum deformational shrinkage so as to minimize curling and cupping of easily deformed substrates.
- an ultraviolet-curable liquid coating composition comprises: (A) a cationically curable polyepoxide; (B) an acrylate-functional compound carrying at least one reactive group selected from: (1) a monoacrylate-functional compound carrying at least two primary hydroxy groups; and (2) an epoxy-functional monoacrylate in admixture with a compound carrying a plurality of primary hydroxyl groups; (C) an acrylate-functional liquid, preferably a monoacrylate, in an amount providing coating viscosity; and (D) a catalyst component capable of initiating, on ultraviolet exposure, both the conventional free-radical polymerization of ethylenically unsaturated monomers, and the cationic polymerization of polyepoxides in the presence of a compound carrying the primary hydroxy group.
- This catalyst component usually comprises a radiation sensitive aromatic onium salt capable of releasing a Lewis acid when exposed to radiant energy, preferably a triaryl sulfonium or iodinium salt.
- the ratio of epoxy groups provided by component (A) to primary hydroxy groups provided by component (B) should be in the range of from 0.5:1 to 6:1, preferably from 1.5:1 to 4:1.
- the coating cures in two stages.
- the first stage the acrylate-functional compound polymerizes rapidly by free-radical mechanism, but the shrinkage tendency of the free-radical cure is relieved because the coating has not yet solidified because the cationically curable polyepoxide is present as an unreacted diluent.
- the second stage the cationically curable polyepoxide cures slowly with the primary hydroxy groups which are present to provide the desired fully solidified protective coating.
- the cationic cure does not exhibit the undesirable shrinkage which characterizes the free radical cure.
- the coatings of this invention retain much of the rapid curing character of the acrylate coating systems, and rapid ultraviolet exposures can be used.
- polyepoxides which are cationically curable and used in this invention as component (A) constitute a known class of materials. Those based on hydrogenated bisphenol, such as Eponex DRH 1511 and DRH 1510, are useful herein, but cycloaliphatic liquid epoxy resins, such as Bakelite ERL 4221 and ERL 4299, are also useful. Hydantoin-based polyepoxides are also useful and available from Ciba-Geigy. These may be used alone, or in combination with glycidyl ethers of a bisphenol, such as the Shell products Epon 828 and Epon 1001, or the Ciba-Geigy product Araldite 6010.
- Component (B) in this invention can be selected from two categories, as previously noted.
- the first category we have monoacrylates containing a plurality of primary hydroxy groups. These are illustrated by acrylate esters and ethers of polyhydric alcohols containing three or more hydroxy groups.
- acrylate esters and ethers of polyhydric alcohols containing three or more hydroxy groups are illustrated by acrylate esters and ethers of polyhydric alcohols containing three or more hydroxy groups.
- an acrylate ester formed by reacting one molar proportion of acrylic acid or 2-hydroxyethyl acrylate with one molar proportion of trimethylol propane or pentaerythritol.
- the ether of one mole of 2-ethoxy acrylate with one mole of trimethylol propane will be used as illustrative.
- epoxy monoacrylates such as glycidyl acrylate or the monoacrylate of a low molecular weight diglycidyl ether of a bisphenol, such as the commercial product Epon 828 sold by Shell Chemical Company.
- Epon 828 sold by Shell Chemical Company.
- a polyhydric alcohol containing at least two hydroxy groups such as ethylene glycol, diethylene glycol, 1,4-butane diol, 1,6-hexane diol, trimethylol propane, and the like.
- the coating compositions of this invention are preferably of relatively low viscosity to enable spin coating to be used, for this is a particularly effective procedure for coating the polycarbonate discs under consideration. Even for general coating application, an acrylate liquid should be added to adjust viscosity. These materials are entirely conventional, and are illustrated by low viscosity acrylate liquids such as ethoxy acrylate, ethoxyethoxyethyl acrylate, butyl acrylate, phenoxyethyl acrylate, and the like.
- compositions of this invention are catalyzed by a catalyst component capable of initiating, on ultraviolet exposure, both the conventional free-radical polymerization of ethylenically unsaturated monomers, and the cationic polymerization of polyepoxides in the presence of a compound carrying the primary hydroxy group.
- Photoinitiators useful for the ultraviolet-initiated cationic cure of appropriate polyepoxides are known. These are fully disclosed in U.S. Pat. No. 4,156,035, the disclosure of which is incorporated by reference. This patent indicates that any radiation sensitive aromatic onium salt of a group VIa element capable of releasing a Lewis acid when exposed to radiant energy may be used, triphenyl sulfonium fluroborate, triphenyl sulfonium hexafluorophosphate and triphenyl sulfonium hexafluoroantimonate being mentioned to illustrate the character of the known onium salts which may be used.
- This patent uses these onium salts in combination with what it describes as carbonyl type photoinitiators, i.e., the aldehyde and ketone carbonyl compounds having at least one aromatic nucleus attached directly to the carbonyl group, such as benzophenone, acetophenone, or many others listed in the patent.
- Diaryliodonium salts such as the 3M product FC 509, are also contemplated, and these are normally used in combination with a ketonic photosensitizer, especially benzophenone.
- Other photosensitizers are illustrated by chlorothioxanthone, isopropylthioxanthone, thioxanthone, xanthone, and the like. Benzophenone is preferred because of its greater solubility and lower cost.
- iodonium salts normally require ketonic photosensitizers, it is preferred to employ triaryl sulfonium salts, such as the 3M product FC 508 and UVE-1014 from General Electric Co. These sulfonium salts do not require ketonic photosensitizer.
- the General Electric product is especially preferred and is described as a triphenyl sulfonium antimony hexafluoride which is available in a 50% solution in propylene carbonate.
- These coatings are applied to the metallized surface of a metallized polycarbonate disc.
- the disc with the coating material thereon is spun to distribute the coating over the surface of the disc, and the wet-coated surface is then exposed to ultraviolet light to cure the same.
- the shrinkage encountered when the usual acrylate coatings are employed is avoided by the various compositions which have been illustrated herein.
- the disc coated in this example has a metallized surface, but this is not essential.
Abstract
An ultraviolet-curable liquid coating composition which possesses minimal substrate deformational shrinkage on cure is disclosed in which (A) a cationically curable polyepoxide having a 1,2-epoxy equivalency of at least 1.3 is used in admixture with (B) an acrylate-functional compound which is either (1) a monoacrylate-functional compound carrying at least two primary hydroxy groups; or (2) an epoxy-functional monoacrylate in admixture with a compound carrying a plurality of primary hydroxyl groups. An acrylate-functional liquid (C), preferably a monoacrylate, is used to provide coating viscosity, and a catalyst component capable of initiating, on ultraviolet exposure, both the conventional free-radical polymerization of ethylenically unsaturated monomers, and the cationic polymerization of polyepoxides in the presence of a compound carrying the primary hydroxy group. This catalyst component usually comprises a radiation sensitive aromatic onium salt capable of releasing a Lewis acid when exposed to radiant energy, together with an effective amount of a ketonic free radical photoinitiator when the onium salt is ineffective to perform this function. This provides a two stage cure in which shrinkage is minimized to control curling and cupping of easily deformable coated substrates.
Description
1. Technical Field
This invention relates to liquid ultraviolet-curable coating compositions which cure to a solid adherent film with minimum deformational shrinkage so as to minimize curling and cupping of easily deformed substrates.
2. Background Art
It is desirable to protect easily deformed substrates, such as polycarbonate discs of the type intended to be read using laser light, using ultraviolet-curing coatings. However, when the usual acrylate-based ultraviolet-curable coatings are used, the free-radical cure proceeds in a single stage to cause extensive shrinkage which deforms the substrate, e.g., it causes the polycarbonate disc to curl or cup. As a result, the usual acrylate-based ultraviolet-curable coatings are not useful on such easily deformable substrates. We know of nothing to suggest how the rapid cure of acrylate-based ultraviolet-curable coatings can be maintained without encountering the shrinkage which cannot be tolerated when the substrate is easily deformed.
Of interest to this invention is U.S. Pat. No. 4,158,035 issued to W. R. Grace and Co. in the names of Jung-Hsien Tsao and Arthur D. Ketley. This patent, issued on May 22, 1979, discloses radiation curable coatings comprising mixtures of epoxy resin and di- or poly-acrylate or methacrylate monomers in combination with a catalyst system capable of initiating both free radical polymerization and cationic polymerization upon ultraviolet exposure. This is done with a combination of a carbonyl type photoinitiator and an aromatic onium salt which releases a Lewis acid on ultraviolet exposure. However, this patent does not consider the problem of shrinkage, it does not employ a polyhydric alcohol containing a plurality of primary hydroxy groups, and it relies upon polyacrylates for the free radical cure whereas monoacrylates are used herein.
In accordance with this invention, an ultraviolet-curable liquid coating composition comprises: (A) a cationically curable polyepoxide; (B) an acrylate-functional compound carrying at least one reactive group selected from: (1) a monoacrylate-functional compound carrying at least two primary hydroxy groups; and (2) an epoxy-functional monoacrylate in admixture with a compound carrying a plurality of primary hydroxyl groups; (C) an acrylate-functional liquid, preferably a monoacrylate, in an amount providing coating viscosity; and (D) a catalyst component capable of initiating, on ultraviolet exposure, both the conventional free-radical polymerization of ethylenically unsaturated monomers, and the cationic polymerization of polyepoxides in the presence of a compound carrying the primary hydroxy group. This catalyst component usually comprises a radiation sensitive aromatic onium salt capable of releasing a Lewis acid when exposed to radiant energy, preferably a triaryl sulfonium or iodinium salt. The ratio of epoxy groups provided by component (A) to primary hydroxy groups provided by component (B) should be in the range of from 0.5:1 to 6:1, preferably from 1.5:1 to 4:1.
When the liquid coatings of the above composition are exposed to ultraviolet light, the coating cures in two stages. In the first stage, the acrylate-functional compound polymerizes rapidly by free-radical mechanism, but the shrinkage tendency of the free-radical cure is relieved because the coating has not yet solidified because the cationically curable polyepoxide is present as an unreacted diluent. In the second stage, the cationically curable polyepoxide cures slowly with the primary hydroxy groups which are present to provide the desired fully solidified protective coating. However, the cationic cure does not exhibit the undesirable shrinkage which characterizes the free radical cure.
On the other hand, the coatings of this invention retain much of the rapid curing character of the acrylate coating systems, and rapid ultraviolet exposures can be used.
The polyepoxides which are cationically curable and used in this invention as component (A) constitute a known class of materials. Those based on hydrogenated bisphenol, such as Eponex DRH 1511 and DRH 1510, are useful herein, but cycloaliphatic liquid epoxy resins, such as Bakelite ERL 4221 and ERL 4299, are also useful. Hydantoin-based polyepoxides are also useful and available from Ciba-Geigy. These may be used alone, or in combination with glycidyl ethers of a bisphenol, such as the Shell products Epon 828 and Epon 1001, or the Ciba-Geigy product Araldite 6010. These commercial products are all of known composition, and can be described as resinous polyepoxides having a 1,2-epoxy equivalency of at least 1.3. Polyepoxides based on phenolic novalac resins and epoxidized polybutadienes, are also useful, and the pure "electronic grades" of phenolic novalacs are presently preferred. These "electronic grades" contain very low levels of hydrolyzable chlorine. The epoxidized novalacs may be used alone or in admixture with the hydrogenated bisphenol-based polyepoxides or the cycloaliphatic polyepoxides. Even monoepoxides may be present, such as Cardura E from Shell Chemical Company which is a glycidyl ester of neodecanoic acid.
Component (B) in this invention can be selected from two categories, as previously noted. In the first category we have monoacrylates containing a plurality of primary hydroxy groups. These are illustrated by acrylate esters and ethers of polyhydric alcohols containing three or more hydroxy groups. Thus, one may use an acrylate ester formed by reacting one molar proportion of acrylic acid or 2-hydroxyethyl acrylate with one molar proportion of trimethylol propane or pentaerythritol. The ether of one mole of 2-ethoxy acrylate with one mole of trimethylol propane will be used as illustrative.
In the second category we have epoxy monoacrylates, such as glycidyl acrylate or the monoacrylate of a low molecular weight diglycidyl ether of a bisphenol, such as the commercial product Epon 828 sold by Shell Chemical Company. These are used in combination with a polyhydric alcohol containing at least two hydroxy groups, such as ethylene glycol, diethylene glycol, 1,4-butane diol, 1,6-hexane diol, trimethylol propane, and the like.
The coating compositions of this invention are preferably of relatively low viscosity to enable spin coating to be used, for this is a particularly effective procedure for coating the polycarbonate discs under consideration. Even for general coating application, an acrylate liquid should be added to adjust viscosity. These materials are entirely conventional, and are illustrated by low viscosity acrylate liquids such as ethoxy acrylate, ethoxyethoxyethyl acrylate, butyl acrylate, phenoxyethyl acrylate, and the like.
The compositions of this invention are catalyzed by a catalyst component capable of initiating, on ultraviolet exposure, both the conventional free-radical polymerization of ethylenically unsaturated monomers, and the cationic polymerization of polyepoxides in the presence of a compound carrying the primary hydroxy group.
Photoinitiators useful for the ultraviolet-initiated cationic cure of appropriate polyepoxides are known. These are fully disclosed in U.S. Pat. No. 4,156,035, the disclosure of which is incorporated by reference. This patent indicates that any radiation sensitive aromatic onium salt of a group VIa element capable of releasing a Lewis acid when exposed to radiant energy may be used, triphenyl sulfonium fluroborate, triphenyl sulfonium hexafluorophosphate and triphenyl sulfonium hexafluoroantimonate being mentioned to illustrate the character of the known onium salts which may be used. This patent uses these onium salts in combination with what it describes as carbonyl type photoinitiators, i.e., the aldehyde and ketone carbonyl compounds having at least one aromatic nucleus attached directly to the carbonyl group, such as benzophenone, acetophenone, or many others listed in the patent. Diaryliodonium salts, such as the 3M product FC 509, are also contemplated, and these are normally used in combination with a ketonic photosensitizer, especially benzophenone. Other photosensitizers are illustrated by chlorothioxanthone, isopropylthioxanthone, thioxanthone, xanthone, and the like. Benzophenone is preferred because of its greater solubility and lower cost.
The onium salts under consideration are more fully disclosed in U.S. Pat. Nos. 4,069,054, 4,069,055, 4,069,054 and 4,423,136.
Since iodonium salts normally require ketonic photosensitizers, it is preferred to employ triaryl sulfonium salts, such as the 3M product FC 508 and UVE-1014 from General Electric Co. These sulfonium salts do not require ketonic photosensitizer. The General Electric product is especially preferred and is described as a triphenyl sulfonium antimony hexafluoride which is available in a 50% solution in propylene carbonate.
______________________________________
Component Weight Percent
______________________________________
Epoxy novolac (2.2 epoxy groups per
44
molecule) [see Note 1]
Ethoxyethoxyethyl acrylate
32
(nonfunctional acrylate diluent)
Trimethylol propane monoethoxy acrylate
20
Triphenyl sulfonium antimony hexafluoride
4
(50% solution in propylene carbonate)
[see Note 2]
______________________________________
Note 1: Ciba Geigy (Ardsley, NY) product DEN 431 may be used.
Note 2: General Electric Company (Schenectady, NY) product UVE1014 may be
used. This is a dual acting catalyst which simultaneously provokes
freeradical polymerization and cationic polymerization upon ultraviolet
exposure.
In this example, 0.25 equivalents of oxirane functionality are reacted with 0.125 equivalents of primary hydroxy in the trimethylol propane monoethoxy acrylate.
______________________________________
Component Weight Percent
______________________________________
Epoxy novolac (2.2 epoxy groups per
44
molecule) [see Note 1]
Ethoxyethoxyethyl acrylate
32
(nonfunctional acrylate diluent)
Diglycidyl ether of bisphenol A
10
(molecular weight 390) monoacrylate
[see Note 3]
Ethylene glycol 10
Triphenyl sulfonium antimony hexafluoride
4
(50% solution in propylene carbonate)
[see Note 2]
______________________________________
Note 1: Ciba Geigy (Ardsley, NY) product DEN 431 may be used.
Note 2: General Electric Company (Schenectady, NY) product UVE1014 may be
used. This is a dual acting catalyst which simultaneously provokes
freeradical polymerization and cationic polymerization upon ultraviolet
exposure.
Note 3: Shell Chemical Company product Epon 828 can be used after reactio
with one molar proportion of acrylic acid.
______________________________________
Component Weight Percent
______________________________________
Cycloaliphatic polyepoxide
54.5
[see Note 4]
Dicaprolactone acrylate
13.6
(nonfunctional acrylate diluent)
Trimethylol propane monoethoxy acrylate
27.4
Triphenyl sulfonium antimony hexafluoride
4.5
(50% solution in propylene carbonate)
[see Note 2]
______________________________________
Note 2: General Electric Company (Schenectady, NY) product UVE1014 may be
used. This is a dual acting catalyst which simultaneously provokes
freeradical polymerization and cationic polymerization upon ultraviolet
exposure.
Note 4: Union Carbide Corporation product UVR 6110 may be used.
These coatings are applied to the metallized surface of a metallized polycarbonate disc. The disc with the coating material thereon is spun to distribute the coating over the surface of the disc, and the wet-coated surface is then exposed to ultraviolet light to cure the same. The shrinkage encountered when the usual acrylate coatings are employed is avoided by the various compositions which have been illustrated herein.
The disc coated in this example has a metallized surface, but this is not essential.
Claims (14)
1. An ultraviolet-curable liquid coating composition which possesses minimal deformational shrinkage on cure comprising: (A) a cationically curable polyepoxide having a 1,2-epoxy equivalency of at least 1.3; (B) an acrylate-functional compound carrying at least one reactive group selected from: (1) a monoacrylate-functional compound carrying at least two primary hydroxy groups; and (2) an epoxy-functional monoacrylate in admixture with a compound carrying a plurality of primary hydroxyl groups; (C) an acrylate-functional liquid, preferably a monoacrylate, in an amount providing coating viscosity; and (D) a catalyst component capable of initiating, on ultraviolet exposure, both the conventional free-radical polymerization of ethylenically unsaturated monomers, and the cationic polymerization of polyepoxides in the presence of a compound carrying the primary hydroxy group, the ratio of epoxy groups provided by component (A) to primary hydroxy groups provided by component (B) being in the range of from 0.5:1 to 6:1.
2. An ultraviolet-curable liquid coating composition as recited in claim 1 in which said cationically curable polyepoxide is an epoxy novalac.
3. An ultraviolet-curable liquid coating composition as recited in claim 1 in which said cationically curable polyepoxide is a cycloaliphatic polyepoxide.
4. An ultraviolet-curable liquid coating composition as recited in claim 1 in which said component (B) is a monoacrylate derivative of trimethylol propane.
5. An ultraviolet-curable liquid coating composition as recited in claim 4 in which said monoacrylate derivative is trimethylol propane monoethoxy acrylate.
6. An ultraviolet-curable liquid coating composition as recited in claim 1 in which said component (B) is a mixture of an epoxy functional monoacrylate and a polyhydric alcohol carrying at least two primary hydroxy groups.
7. An ultraviolet-curable liquid coating composition as recited in claim 6 in which said polyhydric alcohol is ethylene glycol.
8. An ultraviolet-curable liquid coating composition as recited in claim 1 in which said ratio of epoxy groups provided by component (A) to primary hydroxy groups provided by component (B) is in the range of from 1.5:1 to 4:1.
9. An ultraviolet-curable liquid coating composition which possesses minimal deformational shrinkage on cure comprising: (A) a cationically curable polyepoxide having a 1,2-epoxy equivalency of at least 1.3; (B) an acrylate-functional compound carrying at least one reactive group selected from: (1) a monoacrylate-functional compound carrying at least two primary hydroxy groups; and (2) an epoxy-functional monoacrylate in admixture with a compound carrying a plurality of primary hydroxyl groups; (C) an acrylate-functional liquid, preferably a monoacrylate, in an amount providing coating viscosity; and (D) a radiation sensitive aromatic onium salt capable of releasing a Lewis acid when exposed to radiant energy, and an effective amount of a ketonic free radical photoinitiator when said onium salt is ineffective to also perform this function, the ratio of epoxy groups provided by component (A) to primary hydroxy groups provided by component (B) being in the range of from 0.5:1 to 6:1.
10. An ultraviolet-curable liquid coating composition as recited in claim 1 in which said onium salt is a triaryl sulfonium or iodinium salt.
11. An ultraviolet-curable liquid coating composition as recited in claim 10 in which said onium salt is a triphenyl sulfonium antimony hexafluoride.
12. A method of coating an easily deformable substrate with a liquid ultraviolet curable coating composition which cures to a solid adherent film with minimum deformational shrinkage comprising applying the liquid coating composition of claim 1 and exposing the applied coating to ultraviolet light.
13. A method as recited in claim 11 in which said deformable substrate is a polycarbonate disc.
14. A method as recited in claim 12 in which said disc is spun to spread said liquid coating on said disc.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/841,216 US4657779A (en) | 1986-03-19 | 1986-03-19 | Shrinkage-resistant ultraviolet-curing coatings |
| PCT/US1987/000532 WO1987005540A1 (en) | 1986-03-19 | 1987-03-16 | Shrinkage-resistant ultraviolet-curing coatings |
| CA000532391A CA1289688C (en) | 1986-03-19 | 1987-03-18 | Shrinkage-resistant ultraviolet-curing coatings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/841,216 US4657779A (en) | 1986-03-19 | 1986-03-19 | Shrinkage-resistant ultraviolet-curing coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4657779A true US4657779A (en) | 1987-04-14 |
Family
ID=25284329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/841,216 Expired - Fee Related US4657779A (en) | 1986-03-19 | 1986-03-19 | Shrinkage-resistant ultraviolet-curing coatings |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4657779A (en) |
| CA (1) | CA1289688C (en) |
| WO (1) | WO1987005540A1 (en) |
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| US4751103A (en) * | 1986-11-13 | 1988-06-14 | Ashland Oil, Inc. | Epoxy primers for polyurethane structural adhesives |
| US4863757A (en) * | 1987-02-06 | 1989-09-05 | Key-Tech, Inc. | Printed circuit board |
| US4950696A (en) * | 1987-08-28 | 1990-08-21 | Minnesota Mining And Manufacturing Company | Energy-induced dual curable compositions |
| US4952612A (en) * | 1987-08-28 | 1990-08-28 | Minnesota Mining And Manufacturing Company | Energy-induced curable compositions |
| US5006397A (en) * | 1987-02-06 | 1991-04-09 | Key-Tech, Inc. | Printed circuit board |
| US5047260A (en) * | 1987-02-06 | 1991-09-10 | Key-Tech, Inc. | Method for producing a shielded plastic enclosure to house electronic equipment |
| US5057551A (en) * | 1988-03-02 | 1991-10-15 | Henkel Kommanditgesellschaft Auf Aktien | Adhesives that continue to harden in darkness after photoinitiation |
| US5070002A (en) * | 1988-09-13 | 1991-12-03 | Amp-Akzo Corporation | Photoimageable permanent resist |
| US5086086A (en) * | 1987-08-28 | 1992-02-04 | Minnesota Mining And Manufacturing Company | Energy-induced curable compositions |
| US5147900A (en) * | 1987-08-28 | 1992-09-15 | Minnesosta Mining And Manufacturing Company | Energy-induced dual curable compositions |
| US5147727A (en) * | 1990-02-06 | 1992-09-15 | Isp Investments Inc. | Aryloxy polyvinyl ethers |
| US5178988A (en) * | 1988-09-13 | 1993-01-12 | Amp-Akzo Corporation | Photoimageable permanent resist |
| US5252694A (en) * | 1992-01-22 | 1993-10-12 | Minnesota Mining And Manufacturing Company | Energy-polymerization adhesive, coating, film and process for making the same |
| WO1995017476A1 (en) * | 1993-12-23 | 1995-06-29 | Basf Lacke + Farben Ag | Radiation-curable protective lacquer, especially for metallised surfaces |
| US5521227A (en) * | 1990-04-23 | 1996-05-28 | Minnesota Mining And Manufacturing Company | Energy curable cationcally and free-radically polymerizable pressure-sensitive compositions |
| WO1997042549A1 (en) * | 1996-05-09 | 1997-11-13 | Dsm N.V. | Photosensitive resin composition for rapid prototyping and a process for the manufacture of 3-dimensional objects |
| US5721289A (en) * | 1994-11-04 | 1998-02-24 | Minnesota Mining And Manufacturing Company | Stable, low cure-temperature semi-structural pressure sensitive adhesive |
| EP0831127A1 (en) * | 1995-05-12 | 1998-03-25 | Asahi Denka Kogyo Kabushiki Kaisha | Stereolithographic resin composition and stereolithographic method |
| US5856373A (en) * | 1994-10-31 | 1999-01-05 | Minnesota Mining And Manufacturing Company | Dental visible light curable epoxy system with enhanced depth of cure |
| WO2000042115A1 (en) * | 1999-01-13 | 2000-07-20 | Dsm N.V. | Photo curable adhesive composition |
| US6294241B1 (en) * | 1993-02-19 | 2001-09-25 | Giesecke & Devrient Gmbh | Security document and method of producing it |
| US6677390B1 (en) * | 1999-08-02 | 2004-01-13 | Nippon Soda Co., Ltd. | Photocurable composition containing iodonium salt compound |
| US20040063804A1 (en) * | 2001-03-30 | 2004-04-01 | Masaaki Takeda | Thermosetting adhesive |
| US20040113243A1 (en) * | 1998-09-03 | 2004-06-17 | Guy Blalock | UV cured polymeric semiconductor die coating |
| US6765037B2 (en) * | 2001-11-03 | 2004-07-20 | Dymax Corporation | Photopolymerizable epoxy composition |
| US20050228064A1 (en) * | 2000-02-08 | 2005-10-13 | Huntsman Advanced Materials Americas Inc. | Liquid radiation-curable composition, especially for stereolithography |
| US20060060504A1 (en) * | 2004-09-08 | 2006-03-23 | Vierheilig Albert A | Additives for metal contaminant removal |
| USRE39106E1 (en) | 1995-06-07 | 2006-05-23 | Dsm Ip Assets B.V. | Photohardenable epoxy composition |
| WO2006118532A1 (en) * | 2005-05-04 | 2006-11-09 | Perstorp Specialty Chemicals Ab | Hybrid radiation curable composition and use thereof |
| CN103718108A (en) * | 2011-07-31 | 2014-04-09 | 日本化药株式会社 | Photosensitive resin composition and cured product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2700171B1 (en) * | 1993-01-07 | 1995-02-24 | Vetrotex France Sa | Process for the preparation of glass-resin prepregs intended for the manufacture of composite parts. |
| FR2727972B1 (en) * | 1994-12-13 | 1997-01-31 | Vetrotex France Sa | SIZING COMPOSITION FOR GLASS WIRES, PROCESS USING THIS COMPOSITION AND RESULTING PRODUCTS |
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| US4156035A (en) * | 1978-05-09 | 1979-05-22 | W. R. Grace & Co. | Photocurable epoxy-acrylate compositions |
| US4218531A (en) * | 1978-02-08 | 1980-08-19 | Minnesota Mining And Manufacturing Company | Addition of ethylenically unsaturated materials to control odor in photopolymerizable epoxy compositions |
| US4245029A (en) * | 1979-08-20 | 1981-01-13 | General Electric Company | Photocurable compositions using triarylsulfonium salts |
| US4256828A (en) * | 1975-09-02 | 1981-03-17 | Minnesota Mining And Manufacturing Company | Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials |
| US4303696A (en) * | 1975-05-07 | 1981-12-01 | Design Cote Corp. | Radiation curing of prepolymer coating compositions |
| US4423136A (en) * | 1977-08-05 | 1983-12-27 | General Electric Company | Free radical curable resin compositions containing triarylsulfonium salt |
| JPS5921542A (en) * | 1982-07-23 | 1984-02-03 | Nitto Electric Ind Co Ltd | Coating material for optical glass fiber |
| US4576850A (en) * | 1978-07-20 | 1986-03-18 | Minnesota Mining And Manufacturing Company | Shaped plastic articles having replicated microstructure surfaces |
| US4582885A (en) * | 1978-07-20 | 1986-04-15 | Minnesota Mining And Manufacturing Company | Shaped plastic articles having replicated microstructure surfaces |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4245828A (en) * | 1978-05-08 | 1981-01-20 | Blackhawk Systems, Inc. | Apparatus for fabrication of metal buildings |
-
1986
- 1986-03-19 US US06/841,216 patent/US4657779A/en not_active Expired - Fee Related
-
1987
- 1987-03-16 WO PCT/US1987/000532 patent/WO1987005540A1/en unknown
- 1987-03-18 CA CA000532391A patent/CA1289688C/en not_active Expired - Fee Related
Patent Citations (9)
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|---|---|---|---|---|
| US4303696A (en) * | 1975-05-07 | 1981-12-01 | Design Cote Corp. | Radiation curing of prepolymer coating compositions |
| US4256828A (en) * | 1975-09-02 | 1981-03-17 | Minnesota Mining And Manufacturing Company | Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials |
| US4423136A (en) * | 1977-08-05 | 1983-12-27 | General Electric Company | Free radical curable resin compositions containing triarylsulfonium salt |
| US4218531A (en) * | 1978-02-08 | 1980-08-19 | Minnesota Mining And Manufacturing Company | Addition of ethylenically unsaturated materials to control odor in photopolymerizable epoxy compositions |
| US4156035A (en) * | 1978-05-09 | 1979-05-22 | W. R. Grace & Co. | Photocurable epoxy-acrylate compositions |
| US4576850A (en) * | 1978-07-20 | 1986-03-18 | Minnesota Mining And Manufacturing Company | Shaped plastic articles having replicated microstructure surfaces |
| US4582885A (en) * | 1978-07-20 | 1986-04-15 | Minnesota Mining And Manufacturing Company | Shaped plastic articles having replicated microstructure surfaces |
| US4245029A (en) * | 1979-08-20 | 1981-01-13 | General Electric Company | Photocurable compositions using triarylsulfonium salts |
| JPS5921542A (en) * | 1982-07-23 | 1984-02-03 | Nitto Electric Ind Co Ltd | Coating material for optical glass fiber |
Cited By (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4751103A (en) * | 1986-11-13 | 1988-06-14 | Ashland Oil, Inc. | Epoxy primers for polyurethane structural adhesives |
| US5006397A (en) * | 1987-02-06 | 1991-04-09 | Key-Tech, Inc. | Printed circuit board |
| US4863757A (en) * | 1987-02-06 | 1989-09-05 | Key-Tech, Inc. | Printed circuit board |
| US5047260A (en) * | 1987-02-06 | 1991-09-10 | Key-Tech, Inc. | Method for producing a shielded plastic enclosure to house electronic equipment |
| US5147900A (en) * | 1987-08-28 | 1992-09-15 | Minnesosta Mining And Manufacturing Company | Energy-induced dual curable compositions |
| US4952612A (en) * | 1987-08-28 | 1990-08-28 | Minnesota Mining And Manufacturing Company | Energy-induced curable compositions |
| US5086086A (en) * | 1987-08-28 | 1992-02-04 | Minnesota Mining And Manufacturing Company | Energy-induced curable compositions |
| US5326621A (en) * | 1987-08-28 | 1994-07-05 | Minnesota Mining And Manufacturing Company | Energy-induced dual curable compositions |
| US4950696A (en) * | 1987-08-28 | 1990-08-21 | Minnesota Mining And Manufacturing Company | Energy-induced dual curable compositions |
| US5376428A (en) * | 1987-08-28 | 1994-12-27 | Minnesota Mining And Manufacturing Company | Energy-induced dual curable compositions |
| US5057551A (en) * | 1988-03-02 | 1991-10-15 | Henkel Kommanditgesellschaft Auf Aktien | Adhesives that continue to harden in darkness after photoinitiation |
| US5070002A (en) * | 1988-09-13 | 1991-12-03 | Amp-Akzo Corporation | Photoimageable permanent resist |
| US5178988A (en) * | 1988-09-13 | 1993-01-12 | Amp-Akzo Corporation | Photoimageable permanent resist |
| US5147727A (en) * | 1990-02-06 | 1992-09-15 | Isp Investments Inc. | Aryloxy polyvinyl ethers |
| US5521227A (en) * | 1990-04-23 | 1996-05-28 | Minnesota Mining And Manufacturing Company | Energy curable cationcally and free-radically polymerizable pressure-sensitive compositions |
| US5399637A (en) * | 1992-01-22 | 1995-03-21 | Minnesota Mining And Manufacturing Company | Energy-polymerizable adhesive, coating, and film |
| US5252694A (en) * | 1992-01-22 | 1993-10-12 | Minnesota Mining And Manufacturing Company | Energy-polymerization adhesive, coating, film and process for making the same |
| US5310840A (en) * | 1992-01-22 | 1994-05-10 | Minnesota Mining And Manufacturing Company | Energy-polymerizable adhesive, coating and film |
| US6294241B1 (en) * | 1993-02-19 | 2001-09-25 | Giesecke & Devrient Gmbh | Security document and method of producing it |
| WO1995017476A1 (en) * | 1993-12-23 | 1995-06-29 | Basf Lacke + Farben Ag | Radiation-curable protective lacquer, especially for metallised surfaces |
| US5739214A (en) * | 1993-12-23 | 1998-04-14 | Basf Lacke + Farben, Ag | Radiation-curable coating of unsaturated prepolymer, epoxy and ketone resin |
| US5856373A (en) * | 1994-10-31 | 1999-01-05 | Minnesota Mining And Manufacturing Company | Dental visible light curable epoxy system with enhanced depth of cure |
| US5721289A (en) * | 1994-11-04 | 1998-02-24 | Minnesota Mining And Manufacturing Company | Stable, low cure-temperature semi-structural pressure sensitive adhesive |
| EP0831127A1 (en) * | 1995-05-12 | 1998-03-25 | Asahi Denka Kogyo Kabushiki Kaisha | Stereolithographic resin composition and stereolithographic method |
| EP0831127A4 (en) * | 1995-05-12 | 1999-12-01 | Asahi Denka Kogyo Kk | Stereolithographic resin composition and stereolithographic method |
| USRE39106E1 (en) | 1995-06-07 | 2006-05-23 | Dsm Ip Assets B.V. | Photohardenable epoxy composition |
| US6251557B1 (en) | 1996-05-09 | 2001-06-26 | Dsm N.V. | Photosensitive resin composition for rapid prototyping and a process for the manufacture of 3-dimensional objects |
| WO1997042549A1 (en) * | 1996-05-09 | 1997-11-13 | Dsm N.V. | Photosensitive resin composition for rapid prototyping and a process for the manufacture of 3-dimensional objects |
| US20040113243A1 (en) * | 1998-09-03 | 2004-06-17 | Guy Blalock | UV cured polymeric semiconductor die coating |
| WO2000042115A1 (en) * | 1999-01-13 | 2000-07-20 | Dsm N.V. | Photo curable adhesive composition |
| US6677390B1 (en) * | 1999-08-02 | 2004-01-13 | Nippon Soda Co., Ltd. | Photocurable composition containing iodonium salt compound |
| US20050228064A1 (en) * | 2000-02-08 | 2005-10-13 | Huntsman Advanced Materials Americas Inc. | Liquid radiation-curable composition, especially for stereolithography |
| US20040063804A1 (en) * | 2001-03-30 | 2004-04-01 | Masaaki Takeda | Thermosetting adhesive |
| US6765037B2 (en) * | 2001-11-03 | 2004-07-20 | Dymax Corporation | Photopolymerizable epoxy composition |
| US20060060504A1 (en) * | 2004-09-08 | 2006-03-23 | Vierheilig Albert A | Additives for metal contaminant removal |
| US8197669B2 (en) | 2004-09-08 | 2012-06-12 | Intercat, Inc. | Additives for metal contaminant removal |
| WO2006118532A1 (en) * | 2005-05-04 | 2006-11-09 | Perstorp Specialty Chemicals Ab | Hybrid radiation curable composition and use thereof |
| CN103718108A (en) * | 2011-07-31 | 2014-04-09 | 日本化药株式会社 | Photosensitive resin composition and cured product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1289688C (en) | 1991-09-24 |
| WO1987005540A1 (en) | 1987-09-24 |
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